Process for breaking petroleum emulsions employing certain oxyalkylated glucoses



July 12, 1960 M. DE GROOTE ETAL 2,944,980

PROCESS FOR BREAKING PETROLEUM EMULSIONS EMPLOYING CERTAIN OXYALKYLATED GLUCOSES Filed May 24, 1954 BUTYLENE OXIDE I00 '4 c 15 14 u I6 B ll M/V V\/ W A ETHYLENE OXiDE IOOZ NVENT RS PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN OXYALKYLATED GLUCOSES Melvin De Groote, University City, and Owen H. Pettingill, Kirkwood, Mo., assignors to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware Filed May 24,19s4,ser.No.4s1,7s9

20 Claims. (C 252-331 separating emulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively-soft waters or Weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities particularly inorganic salts, from pipelineoil.

- More specifically thengthe present invention is concerned With a process for breaking petroleum'ernulsions employing a demulsifier including .a'cogeneric mixture of a homologous series of glycol ethers of glucose. I The cogeneric mixture is derived exclusively from glucose, ethylene oxide and butylene oxide in such weight'proportions so the average composition of saidcogeneric mixture stated in'terms of initial reactants lies approximately within the -sided figure of the accompanying drawing in which the minimum glucose content is at least 1.5% and which S-sided figure is identified by the fact that its area lies within the straight lines connecting A, B, C, D, and H.

We have found that when glucose is combined with butylene oxide and ethylene oxide in certain proportions and particularly When the butylene oxideis employed first, followed by use of ethylene oxide and more especially if the butylene oxide employed is one of the straight chain isomers.

. l o a V or a mixture of the two and if the composition falls within the limits indicated bythe' 5-sided figure on the I Patented July 12, 1960 with 5 parts by weight of butylene oxide and 85 parts by weight of ethylene oxide. In another series 1.5 parts by weight of glucose have been reacted with 13.5 parts by weight of butylene oxide and 85 parts by weight of ethylene oxide. Similarly, in another series the following combinations have been used: 1.5 parts of glucose combined with 58.5 parts by weight of butylene oxide and 40 parts by weight of ethylene oxide; 20 parts by weight of glucose, reacted with 40 parts by weight of butylene oxide and then with 40 parts by weight of ethylene oxide. In another series 20 parts by weight of glucose were reacted with 10 parts by weight of butylene oxide and then 70 parts by Weight of ethylene oxide.

It is of interest to note in some instances as little as 1.5 parts of glucose may be combined with 98.5 parts of the two oxides to produce very valuable derivatives.

We have also found that where part of the butylene oxide is replaced by propylene oxide, i.e., Where a combination of glucose, butylene oxide, propylene oxide and ethylene oxide are used, elfective and valuable surfaceactive agents can also be obtained. This, however, represents a separate invention. V

For the purpose of resolving petroleum emulsions of the water-in-oil type we prefer to employ oxyalkylated derivatives, which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have sufficient hydrophile'character to meet at least the test set forth in US. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. --In said patent such test for emulsification using a water-insoluble solvent, generallyxylene, is described as an index of surface activity.

The above mentioned test, i.e., a conventional. emulsification test, simply means that the preferred product for demulsification is soluble in a solvent having hydrophobe properties or in an oxygenated water insoluble or even a fraction of a Water-soluble hydrocarbon solvent and that when shaken with-water the product may remain inthe nonaqueous solvent or, for that matter it may pass into. the aqueous solvent.- In other words,

although it is xylene soluble, for example, it may also be water soluble to. an equal or greater degree.

, For purposeof convenience what is said hereinafter will be divided into three parts: Part 1 is concerned with the oxyalkylation of glucose in general{ Part 2 is concerned with the oxyalkylation of glucose using two difierent oxides, i.e., butylene oxideand ethhereto attached triangular chart, said'derivatives are of w in the resolution of'petroleum emulsions of the water-in-' oil type.

In a general way the compounds which'have been ylene oxide so as to produce derivatives falling within certain composition limitations hereinafter noted, in

detail. For convenience, Part 2 is divided into two sections, Section A is concerned with oxybutylation and oxyethylation broadly, and Section B is concerned with the particular compositions corresponding to the herein specified compositions and illustrate such combinations;

Part 3 is concerned with the resolution ofpetroleum emulsionsof the water-in-oil type by means of the previously described chemical compounds.

7 PART 1 At the present time there is available butylene oxide which includes isomeric mixtures, for instance, one manufacturer has previously supplied a mixed butylene oxide which is in essence a mixture of l-butene oxide, Z-butene found most efiective and fall within the'limits' of the oxide isomers and approximately 10% isobutylene oxide. Another manufacturer has supplied an oxide which is roughly a fifty-fifty mixture of the cisand trans-isomers of Z-butene oxide.

There is also available a butyleneoxide which is characterized as straight chain isomers being a mixture of the 1,2 andthe 2,3 isomers and substantially free from the-isobutylene oxide. i

- This latter product appears to consist of of the 1,2 isomer and 15% of the mixed 2,3 cisand 2,3 transisomer. We have obtained the best results by using an oxide that is roughly 80% or more of the 1,2 isomer and with either none, or just a few percent if any, of the isobutylene oxide, the difierence being either form of the 2,3 or a mixture of the two forms.

Our preference is to use an oxide substantially free from the isobutylene oxide, or at least having minimum amounts of isobutylene oxide present.

Since the varying solubility of difierent butanols is well known, it is unnecessary to comment on the effect that the varying structure has on solubility of derivatives obtained by butylene oxide. Purely by way of example, the applicants have tested the solubility of the first two available butylene oxides and noted in one instance the butylene oxide would dissolve to the extent of 23 grams in 100 grams of water, whereas the other butylene oxide would only dissolve to the extent of 6 grams in 100 grams of water. These tests were made at 25 C.

As to further reference in regard to the isomeric butylene oxides see Chemistry of Carbon Compounds, vol ume I, part A, Aliphatic Compounds, edited by E. H. Rodd, Elsevier Publishing Company, New York, 1951, page 671.

As to the difference in certain proportions of the cisand trans-form of straight chain isomers 2,3-epoxybutane see page 341 of A Manual of Organic Chemistry, voltime 1, G. MalcolmDyson, Longmans, Green and Company, New York, 1950.

Reference to butylene oxide herein of course is to the compound or compounds having the oxirane ring and thus excludes 1,4-butylene oxide (tetrahydrofurane) or a trimethylene ring compound.

When reference is made to the oxides, for instance, ethylene oxide and butylene oxide, one can use the cor,- responding carbonates. Ethylene carbonate is available commercially. Butylene carbonate, or the carbonate corresponding to. a particular oxide, is not. available commercially but can be prepared by the usual methods in the laboratory. For this reason further reference to the alkylene carbonates will be ignored although it is under-, stood when oxyethylation takes place by means of ethylene carbonate one could, of course, use butylene car-. bonate for oxybutylation.

In the present invention we have found that outstanding products are obtained by the use of certain preferred butylene oxides, i.e., those entirely free or substantially free (usually 1% or less). and composed of approximately 85% or more of the 1,2 isomer with the remainder, if any, being the 2,3 isomer.

Inv the preparation of the outstanding compounds we have studiously avoided the presence of the isobutylene oxide as far as practical. When any significant amount of isobutylene oxide happens to be present, the results are not as satisfactory regardless of the point when the butylene oxide is introduced. One explanation may be the following. The initial oxybutylation which may be simplified by reference to a monohydric alcohol, produces a tertiary alcohol. Thus the oxybutylation in the presence of alkaline catalyst may be shown thus:

Further oxyalkylation becomes difficult when a tertiary alcohol is involved although the literature records successful oxyalkylation of tertiary alcohols. This does not necessarily apply when oxyalkylation takes place in the presence of an acidic catalyst, for instance, a metallic chloride such as ferric chloride, stannic chloride, aluminum chloride, etc.

The difficulty is that there may be some tendency on the part of glucose to decompose. The decomposition products probably are still'hydroxylated in part and if it does happen to occur oxyalkylation would then involve glucose and hydroxyl containing glucose composition products. We have tried procedures using an alkaline catalyst and glucose employing 4 to 6 moles of isobutylene oxide per mole of glucose. Afterwards an amount of acid was added equal to the amount of caustic employed as a catalyst and the reaction mass dried and then stannic chloride added. Under such circumstances the results suggest more satisfactory oxybutylation as such although the procedure becomes cumbersome, uneconomical and perhaps even impractical.

This, however, seems to be only a partial explanation. Another explanation may rest with the fact that isobutylene oxide may show a tendency to revert back to isobutylene and oxygen and this oxygen may tend to oxidize the terminal hydroxyl radicals. This possibility is purely a matter of speculation, but may account for the reason we obtain much better results using a butylene oxide as specified. In regard to this reaction, i.e., possible conversion of an alkylene oxide back to the olefine and nascent oxygen, see Tall Oil Studies II, Decolorization of Polyethenoxy Tallates With Ozone and Hydrogen Peroxide, V. Karabinos et al., J. Am. Oil Chem. Soc. 31, 71 (1954).

In order to illustrate why the herein contemplated compounds or said products are cogenen'e mixtures and not single chemical compounds, and why they must be described in terms ofmanufacture, and molal ratio or percentage ratio of reactants, reference is made to a monohydric alcohol. Glucose, of course, is a polyhydric alcohol having 6 hydroxyls. However, one need only consider what happens when a monohydric alcohol is subjected to oxyalkylation.

If one selects any hydroxylated compound and subjects such compound to oxyalkylation, such as oxyethylation, it becomes obvious that one is really producing a polymer of the alkylene oxide except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such a compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent which, for sake of convenience, may be indicated as RO(C H O) H. Instead, one obtains a cogeneric mixture of closely related homologues in which the formula may be shown as the following:

wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25 and perhaps less, to a point where It may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Paul J. Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i.e., the ability to describe how to make the product under .consideration and how to repeat such production time after time without difiiculty, it is necessary to resort to some other method of description.

,What has been said inregard to a' monohydric cornpound of course is multiplied many times in th'e'ca'se of a hexahydric compound such as glucose. This is particularly true even in regard to ethylene'oxide alone but becomes even morecomplicated when butylene oxide is used in light o fwhat has been said previously in regard to the isomers of butylene oxide.

. Section A We have found that we can oxybutylate glucose in the same manner that it is conventionally oxypropylated. For example, we have followed thedirections which appear in columns 4, 5, 6, 7' and 8 of U.S. Patent No. 2,626,935, dated January 27, 1953, to De Groote in regard to the oxypropylation of glucose and substituting butylene oxide for propylene oxide in identically the same way. We have completed the reaction as setforth in Examples la through 4a, inclusive. Stirrer speed, temperature, time period, amount of solvent used, amount of catalyst used, and operating pressure were substantially the same.

Other patents include specific information as to the oxypropylation of sugars or similar products including glucose. Actually the procedure is substantially the same Whether one uses propylene, ethylene, or .butylene oxide. Itis not believed any examples are necessary to illustrate such well known procedure but for purpose of illustration the following are included; i 1

Example In The reaction vessel employed was a stainlms steel autostirrer, inlet, outlet, etc., which is conventional in this The capacity was approximately 4 iyp of. apparatus. liters-Q The stirrer operatedat a speed of approximately 25;0 rpm. Therewere charged into the autoclavej '00 grams oiv glucose, 300grams of xylene, and 15- grams of end of the third stepwas 9.25 parts by weight of butylene oxide per weightof glucose. A

7 Example 411 glucose were subjected to oxyethylation in the same man- ..nerdescribed in respect to the oxypropylated glucose in aforementioned US. Patent No. 2,626,935. Indeed, the

f 'one is working with a liquid and also that ethylene oxide is more reactive than butylene oxide.

procedure is comparatively simple for the reason that As a result,

using the same amount of catalyst one can oxyethylate flmore rapidly than usually at a lower pressure. Thereis jnoysubstantial dilference as far as operating procedure goes whether one is oxyethylating oxypropylated glucose or oxybutylated glucose.

- The same procedure using a slurry of finely powdered jglucosein xylene was employed in connection with ethylene oxide and the same mixture on a percentage basis "lwas jo btained as in the above examples where butylene "oxide and glucose were used. 1f @Tjhje same procedures have been employed using other clave with the usual devices, for heating, heat control,

mately fl5*0- C. At this particular time the addition of butylene, oxide was started. The butylene oxide employed' was a mixture of the. straight chain isomer substantially free from isobutylene oxide. It was added continuou'sly at such speed that it was absorbed by the reaction as added. The amount added in this operation was 1500 grams. The time required to add the butylene oxide .was two hours. During this period the-temperature was maintained at 135 to 150 C., using cooling water through the inner' coils when necessary and otherwise applying heat if required. The maximum pessure during the reaction was 50 pounds per square inch. Ignoring the xylene'and sodium methylate and consideringthe .glucose for convenience, the resultant product represents 3 parts'byweight of butylene oxide to one part by weight of. glucose. The xylene present represented approximate- 1y .6 of one part by weight. a j

Example 2 w 7 .reaction mass was transferredto a larger auto clave (capacity 15 liters). Without adding any more solventor any more xylene the procedure wasrepeated so as to add another 1500 grams oi butylene oxide under substantially the same operating conditions but requiringabout 3 hours for the addition. At the end of this step the ratio represented approximately 6 to l (ratioibutylene oxide to glucose).

Example 3a In a third step, instead of adding 1500 grams of butylone oxide, 1625 grams were added. The reaction slowed upand required approximately 6 hours, using/the same .butylene oxides including mixtures having considerable isobutylene oxide and mixtures of the straight chain isomers with greater or lesser amounts ofthe-2,3.isomer. Where reference has been madein Ipreviousexamples to the straight chain isomer, the product used j-was one which. was roughly'85% or more ofthe 1,2 is'onierfland approximately 15% of the 2,3-cis-' and the 2,3-trans-iso mer with substantially none or not over 1% ofthe isobutyleneoxidef I In the preceding procedures one oxide has been added and then the other. One need not follow this procedure. The two oxides can be mixed together in suitable proportions and subsequently subjected to joint oxyalkylation' so as to obtain products coming within the specified limits, In such instances, of course, the oxyalkylation may be described as random oxyalkylation insofar that one cannot determine the exact location of the butylene'oxide 'or ethylene oxide groups. In such instances the procedure again is identically the same as. previously described and, as a matter of fact, we have used such methods in connection with molten sorbitol, and also in connection with glucose. If desired, one may add part of one oxide and all of the other and then return to the use of the first oxide, for instance; or one may use the procedure as previously, adding first some butylene oxide, then ethylene oxide and then the butylene oxide. Or, inversely,.one may add some ethylene oxide, then all butylene oxide' and then the remainder of the ethylene oxide; or either oxide could. be added in portions so that first one oxide is added, then the other, then the first oxide is added again, and

then the second oxide. 'We have found no advantage The changes previously mentioned are of difference in In other words, oxyethylation will take degree only.

i5 place at a. lower temperature, for instance, a top temperature of probably 130 to 135 C. instead of 145 to 150 C. The same weight of ethylene oxide could be added in 75% to 85% of the time required for g. parts of the 5-sided figure, two parts being triangles and the others being two parallelograms and one trapezoid. Likewise, we have calculated the composition for a number of examples within the area of the graph and corbutylene ox1de. The pressure durmg the react1on, 1n- 5 respondmg to pomts 1 to 18, inclusive. Note these data stead of being 35 to 45 pounds as in the case of butylene are included in Table I, immediately following:

TABLE I Tertiary Mixture, Binary Intermediate Mixtures, Points 011 Percent Basis Percent; Basis Boundary of Area Glucose Butylene Ethylene Glucose Butylene Glucose Ethylene Oxide Oxide Oxide Oxide oxide, is apt to be 10 to 15 pounds and at times a little higher. Otherwise, there is no diiference.

Also, if desired, the use of ethylene carbonate is a very convenient way of oxyethylating glucose. In fact, it can be oxyethylated Without the use of pressure. Such procedure, and particularly melting the carbonate first and adding the powdered glucose slowly permits the production of a reaction mass which is a liquid or which melts readily at comparatively low temperatures to yield a liquid. Such reaction should be conducted in such a way that there is no residual ethylene carbonate when the mass is transferred to an autoclave. One can oxyalkylate using an acid catalyst or an alkaline catalyst or at least in part, without the use of any catalyst although such procedure is extremely slow and uneconomical. In other words, any one of the conventional catalysts used in oxyalkylation may be employed. It is our preference, however, to use an alkaline catalyst such as sodium methylate, caustic soda, or the like.

Actually, finely powdered glucose may contain a trace of moisture. Our preference is to prepare the slurry with an excess of xylene and distill oif one part of the xylene so as to remove any trace of water and then flush out the mass with nitrogen. Even so, there may be a few tenths of a percent of moisture remain although at times examination indicates at the most it is merely a trace.

PART TWO Section B In light of what has been said previously, particularly in Section A, it is obvious that hardly any directions are required to produce the compounds herein specified. However, referring to the composition of the initial reactants based on the S-sided figure in the attached drawing, it will be noted we have calculated the percentage of the three initial reactants for the points A, B, C, D, E, F, G, H, I and I which appear on the boundary of the 5-sided figure and also determine the five sub-divided Note the first column gives the particular point on the boundary of the 5 -sided figure or within the 5-sided figure. Note the next three columns represent the tertiary mixture which corresponds to the initial reactants, to wit, the percentages, by weight, of glucose, butylene oxide and ethylene oxide. Thus it is apparent that one could select any particular point and simply use the appropriate number of pounds of oxide; for instance, in regard to point A all that would be necessary would be to mix 5 pounds of butylene oxide with pounds of ethylene oxide and use the mixture to oxyalkylate 10 pounds of glucose.

Similarly, in Example B, one need only mix 13.5 pounds of butylene oxide with 85 pounds of ethylene oxide and use the mixture to oxyalkylate 1.5 pounds of glucose in the manner previously indicated.

Note the fifth and sixth columns represent binary intermediate mixtures. For instance, in regard to the various points on the boundary and within the S-sided figure, we have calculated the initial mixture using glucose and butylene oxide in the first case, and using glucose and ethylene oxide in the second case, which would be employed for subsequent oxyalkylation to give the particular composition required. Note that a binary intermediate for the preparation of point A can be prepared in any suitable manner involving 66.6% of glucose and 33.4% of butylene oxide. Thus, for example one could use 66.6 pounds of glucose and 33.4 pounds of butylene oxide, or on a larger scale one could use 666 pounds of glucose and 334 pounds of butylene oxide.

Referring now to the tertiary mixture table, it is apparent that for point A glucose and butylene oxide to gether represent 15%, and ethylene oxide 85%. Therefore, one could employ 15 pounds of the binary mixture and react it with 85 pounds of ethylene oxide.

Similarly, in regard to the fifth and sixth columns for point B, the initial mixture involved glucose and butylene oxide, representing 1 0% of glucose and of butylene oxide. If desired 10 pounds of glucose could be reacted with 90 pounds of butylene oxide. Such mixture need only be reacted with ethylene oxidelby reacting 15 pounds of the mixture with 85 pounds of ethylene oxide. "This is obvious from the data in regard to the tertiary mixtures.

7 Referring now to columns 7 and 8, it is obvious one could readily produce an oxyethylated glucose and then resents 1.7% of glucose and 98.3%ethylene oxide. The

mixture so obtained by referring to the tertiary mixture table would be reacted with butylene oxide in the proportion of 86.5 pounds of the mixture and 13.5 pounds of butylene oxide.

As previously pointed out, the oxyalkylation of glucose has :been described in the literature and is described also in detail above. All one need do is employ such conventional oxyalkylation procedure to obtain products corresponding to the compositions as defined. Attention is again directedto the fact that one need not add the entire amount of either oxide at onetime but that a small port-ionof. one could .be. addedand then anothersmall portion of ,the other,.and the process repeatedn Purely .for purposeof illustration, we have prepared examples three different ways corresponding to the com- .positions shown on the chart. 1 In: the first series the butylene oxides and ethylene oxide were mixed; this series is indicated as Aa, Ba, through and including 18a; in the second seriesbutylene oxide was used first followed by ethylene oxide and this series indicated Ab, Eb, through and including 18b; and finally in the third series ethylene oxide was used cfollowed by butylene oxide and the series identified as Ac, Bc, through and including 180.

TABLE II Composition Composition Composition where Butylwhere Ethyl- Oomposition Corresponding where Oxides ene Oxide ene Oxide to Following Point are Mixed Used First Used First Prior to Oxy- Followed by Followed by alkylation Ethylene Butylene Oxide Oxide Aa Ab Ac Ba Bb Be 00 Ob 0c Da Db Dc Ea Eb Ec Fa Fb Fc Ga Gb Gc Ha Hb Hc Ia Ib Ic .T a It: I c la lb 10 2a 2b 20 3a 3b 3c 4a 4b 4c 5a 6b 5c (in. 6b 6c 7a 7b 70 8a 8b 80 9a 9b 9c 10a 10b 100 11a 11b 11a 12a 12b 120 13a 13b 18c 14a 14b 14c 15a 15b 15c 16a 16b 16c 17:; 17b 170 18a 18b 180 The products obtained by the above procedure usually show some colorvarying from a light amber to a pale straw. They can be-bleached in the usual fashion using bleaching clays, charcoal, or an organic bleach, such as peroxide or peracetic acid, or the like.

Such products also have present a small amount of alkaline catalyst which can be removed by conventional 10 mea'ns,'or they can be neutralized by adding anequiw alent amount of acid, such ashydrochloric acid. For many purposes the slight ,aniountof residual alkalinity is not objectionable. i

There are certain variants which can be employed without detracting from the metes and bounds of the invention, .but for all practicalpurposes there is nothing to be gained by such variants and the result is merely increased cost. For instance, any one'of the two oxides can be replaced to a minor percentage and usually to a very small degree, by oxide which would introduce substantially the same group along with a side chain, for

instance, one could employ glycidyl methyl ether, glycidyl 'ethyl ether, glycidyl isopropyl ether, glycidyl butyl' ether orthe like. v

' In the hereto appended .claims reference has been made to glycol ethers of glucose. Actually it well may be that the products should be referredto as polyol ethers of glucose in order to emphasize the fact' that th e'final products of reaction have more than two hydroxyl radicals. However, the" products may be'con-' sidered as hypothetically derived by reaction of glucose with the glycols, such as ethylene glycol, butylene glycol, propylene glycol, or polyglycols. For this reason there seems to be a preference touse the terminology glycol ethers of glucose. a

PART 3 As to the use of conventional demnlsifyingiiagents, reference is made to US. Patent No. 2 526,929, dated January 7, 1953,,toDe Groote and particularlytglart 3.

Everything that appears therein applies withfequal'force as new and desire to secure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of glucose; said cogeneric mixture being derived exclusively from glucose, ethylene oxide and butylene oxide in such weight proportions so the average composition of said cogeneric mixture, stated in terms of initial reactants, lies approximately within the S-sided figure of the accompanying drawing in which the minimum glucose content, is at least 1.5% and which S-sided figure is identified by the fact that its area lies within the straight lines connecting A, B, C, D, and H.

2. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

3. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first.

' 4. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide is substantially free from isobutylene oxide.

5. The process of claim 1 with the proviso that oxyaIkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide consists of or more of the 1,2-isomer and approximately 15% or less of the 2,3-isomeric form, and is substantially free from isobutylene oxide.

6. The process of claim 5 with the proviso that the V reactant, composition falls within the parallelogram I, F, G, and; I.

9.:-The process of claim withtheproviso that the reactant composition falls within the trapezoid I, G, B, and H.

10. The, process of claim 5 with the proviso, that the reactant composition falls within thev triangle H, B, A.

11. A process. for breaking petroleum emulsions of the water-inroil type characterized by subjecting the emulsion to a, demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of glucose; said co: generic mixture being derived exclusively from glucose, ethylene oxide and butylene oxidein such weight proportions so the average composition of said cogeneric mixture, stated in terms of initial reactants, lies approximately within the 5-sided figure of. the accompanying drawing in which the minimum glucose content is at least 1.5% and which 5-sided figure is identified by the fact that its. area lies. within the straight lines connecting A, B, C, D, and H; with the proviso that the hydrophile properties. of said cogeneric mixture in an equal weight of xylene are sufficient to produce an emulsion when said xylene. solution is, shaken vigorously with one to three volumes of water.

12. Thev process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

13. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first.

14. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and

with. the further proviso that the butylene oxide is sub: stantially free from isobutylene oxide.

7 15. The. processof claim 11 with the proviso that oxyalkylation takes. place inpresence of an alkaline catalyst and that the butylene oxide be added first; and.

with thefurther proviso. that the butylene oxide consists of or more of the 1,2-isomer and approximately 15% or less ofthe. 2,3-isomericform, and is substantially free, from isobutylene oxide.

16. The process of claim 15 with the proviso that the reactant composition, falls within the triangular area References Cited in the file of this patent UNITED STATES PATENTS 2,507,910 Keiser et al. May 16, 195.0 2,552,528. De Groote May 15, 1951 2,574,544 De Groote Nov. 13, 1951 2,617,830 Kosmin Nov. 11, 1952 2,624,766v Butler. Jan. 6, 1953 2,662,859. Kirkpatrick Dec. 15, 1953 2,677,700. 1954.

Jackson et al. May 4', 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO A DEMULSIFYING AGENT INCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF GLUCOSE, SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM GLUCOSE, ETHYLENE OXIDE AND BUTYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE, STATED IN TERMS OF INITIAL REACTANTS, LIES APPROXIMATELY WITHIN THE 5-SIDED FIGURE OF TE ACCOMPANYING DRAWING IN WHICH THE MINIMUM GLUCOSE CONTENT IS AT LEAST 1.5% AND WHICH 5-SIDED FIGURE IS IDENTIFIED BY THE FACT THAT ITS AREA LIES WITHIN THE STRAIGHT LINES CONNECTING A,B,C,D,AND H. 